Azo dyestuffs.



UNITED STATES PATENT OFFICE.

OSKAR GU'N'IHER, OF LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNOR TO SYNTHETIC PATENTS C0,, INCL, OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

AZO DYESTUFFS.

1 150 675 Specification of Letters Patent.

No Drawing. Application filed February 16, 1814. Serial No. 818,979.

To all whom it may concern:

Be it known that I, OSKAR Gi'm'rnnn, doctor of philosophy, chemist, citizen of the German Empire, residing at Leverkusen, near Cologne-on-the-Rhine, Germany, have invented new and useful Improvements in Azo Dyestuifs, of which the following is a specification.

I have found that new and valuable dyestuffs capable of being further developed can be obtained by diazotizing the dyestuffs obtainable by coupling a diazoor diazoazo compound with a 1-amino-2-naphthol-ether compound with a free -position and by combining the resulting diazo compound with such a derivative of a 2-a1ninonaphthol sulfonic acid, e. 9.,2-amino-5-naphthol-7-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid as contain a diazotizable amino group in a heteronuclear side chain. By heteronuolear side chain I mean a side chain the nucleus of which comprises dissimilar elements such as carbon and nitrogen. The new products are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water. Upon reduction with stannous chlorid and hydrochloric acid they are broken up into an aromatic amino compound, a 1.4-diamino2- naphtholether compound and a derivative of an amino-beta-amino-alpha-naphthol-betasulfonic acid containing a diazotizable amino group in a heteronuclear side chain.

01 N H N H EDI amino benzoylamino-6-amino-5-naphthol-7- sulfonic acid.

They dye cotton generally in blue to greenish-blue shades, which can be converted by diazotation on fiber and after treatment with suitable developers, such as phenylmethylpyrazolone, aceto-acetic-anilid, phenol, resorcm, etc., into greenish fast shades. They can also be developed with diazotized paranitranilin.

In order to illustrate the new process more fully the following example is given, the parts being by weight The diazo compound obtained from 242 parts of 2.5-dichloroanilin-t-sulfonic acid is combined after the addition of sodium acetate with 267 parts of the 1-amino-2-naphthol-ethyl-ethylether-fi-sulfonic acid dissolved in soda. The resulting intermediate compound is isolated as its sodium salt, further diazotized by means of 69 parts of NaNO,, the diazo compound is filtered ofl", stirred up with Water to a paste and added at 0 to a solution of 358 parts of para-amino-benzoyl-Q-amino-5- naphthol-T-sulfonic acid in an excess of ammonia. The dye is then salted out. It is a dark powder soluble in concentrated sulfuric acid with a greenish-blue coloration; dyeing cotton a bluish-green which after diazotation and on development with methyl-phenylpyrazolone changes into a beautiful yellowish-green. Being developed with diazotized para-nitranilin green shades result. The new dye has in a free state most probably the formula:

Instead of the dichloroanilin-sulfonic acid other diazotizable aromatic amino compounds and aminoazo compounds can be used, 6. 9., 4-chloroanilin-2-sulfonic acid, 4.5-dichlornanilin-Q-sulfosnic acid, 1-naphthylamin-7-sul fonic acid, 2-naphthylamin-5-sulfonic acid, 2-naphthylamin-8-sulfonic acid, l-naphthylamin-3.7-disulfonic acid, aminoazobenzene- Patented Aug. 17, 1915.

disulfonic acid, etc. Instead of the l-amino- 2-naphtholether sulfonic acid this ether itself, etc., can be used. Instead of the paraamino-benzoyl-Zii-aminonaphthol-7-Sulfonic acid generally such heteronuclear derivatives of the said aminonaphthol-sulfonic acids can be used as contain a diazotizable amino group in the heteronuclear side chain, such as meta aminophenyl 1.2 -naphthimidazole-5- oxy-7-sulfonic acid (German Letters Patent 172319), para-aminophenyl-1.2-naphthothiazole-5-oxy-7-sulfonic acid, meta-amino-benzoyl 2 amino-S-naphthol 7 sulfonic acid, metaor para-aminobenzoyl-meta-aminobenzoyl 2 amino 5 naphthol-T-sulfonic acid, para-aminobenzoyl 2 amino-S-naphthol-fisulfonic acid.

I claim 1. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a 1.4-diamino-2- naphtholether compound and a derivative of an amino-beta-amino-alpha-naphthol-betasulfonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

2. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an arcmatic amino sulfonic acid, a lA-diamino-Q- naphtholether compound and a derivative of amino-beta-amino-alpha-naphthol.-beta Suifonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally in blue to greenishblue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

3. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a chloranilin sulfonic acid, a 1.4-diamino-2-naphtholether compound and a derivative of aminn-beta-amino-alpha-naphthol-beta-sulfonic acid containing a diazotizable amino group i as part of a heteronuclear side chain; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

4. The new azo dyestufl's which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an arcmatic amino compounds, a 1.4-diamino-2- naphtholether sulfonic acid and a derivative of amino-beta-amino-alpha-naphthol-betasulfonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally blue to greenishblue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

5. The new azo dyestufl's which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a 1.4-diamino-2- naphtholethylether-6-sulfonic acid and a derivative of amino-beta-amino-alpha-naphthol-beta-sulfonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

6. The new azo dyestufl's which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a L-i-diamino-Q- naphtholether compound and an aminobenzoylamino amino naphthol sulfonic acid; dyeing cotton generally in blue to greenishblue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized paranitranilin, substantially as described.

7. The new azo dyestufls which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a chloranilin sulfonic acid, a 1.4-diamino-2-naphtholethylether-fi-sulfonic acid and a derivative of amino-beta-amino-alphanaphtholbeta-sulfonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally in blue to greenish-blue shades whichcan be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

8. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a chloranilin sulfonic acid, a 1.4-diainino-2-naphtholether sulfonic acid and a derivative of amino beta amino alpha naphthol betasulfonic acid containing a diazotizable amino group as part of a heteronuclear side chain; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

9. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a IA-diamino-Q- naphtholether sulfonic acid and an aminobenzoyl-2-amino-amino naphthol sulfonic acid; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

10. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a 1.4-diamino-2- naphtholethylether-Gsulfonic acid and an aminobenzoyl 2 amino amino naphtholsulfonic acid; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be dewhich is after being dried and pulverized V a dark powder soluble in concentrated sulfuric acid and in water with a greenishblue coloration; yielding upon reduction veloped with diazotized para -nitranilin, substantially as described.

11. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino sulfonic acid, a 1.4-diamino-2-naphtholethylether-B-sulfonic acid and an aminobenzoyl-Q-amino-amino naphtholsulfonic acid; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

12. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stan nous chlorid and hydrochloric acid a chloranilin sulfonic acid, a lA-diaminoQ-naphtholether-sulfonic acid and an aminobenzoyl-2-amino-amino-naphthol-sulfonic acid; dyeing cotton generally in blue to greenishblue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

13. The new azo dyestuffs which are after being dried and pulverized in the shape of theiralkaline salts dark powders soluble in water, yielding upon reduction with stanllOllS chlorid and hydrochloric acid a chloranilin sulfonic acid, a IA-diamino-Q-naphtholethylether-(S-sulfonic acid and an aminobenzoyl-Q-amino-amino naphthol sulfonic acid; dyeing cotton generally in blue to greenish-blue shades which can be converted by diazotation on fiber and after treatment with suitable developers into greenish fast shades, and which can be developed with diazotized para-nitranilin, substantially as described.

14. The new azo dyestuff having in a free state most probably the formula:

with stannous chlorid and hydrochlori: acid 2.5 dichloroanilin 4 sulfonic acid, Lit-diamino-2-ethoxynaphthalene-fi sulfonic acid and 2-para-amino-benzoylamino-fi-arhino-5- naphthol-7-sulfonic acid; dyeing cotton 3 In testimony whereof I have hereunto set bluish-green which after dlazotation and on my hand in the presence of two subscribing development with methylphenyl-pyrazolone witnesses.

changes into a bea ntiful yellowish-green; OSKAR GUNTHER. 5 being developed wlth diazotized para-ni- Witnesses:

tranilin into green shades, substantially as RUDOLF Flzmui'mmn,

described. LOUIS VANDORY.

It is hereby certified that in Letters Patent No. 1,150,675,- gmnted August 17,

1915, upon the application of Oskar Gunther, of Leverkueen, near Cologne, Germany,

for an improvement in Azo Dyestuffs, errors appear in the printed specification requiring eorrection as follows: Page 1, line 48, strike out the word ethyl,"

second occurrence; same page, strike out line 67; and that the said Letters Patent should be read with these corrections therein that the some may conform to the record of the case in the Patent Ofliee.

Signed and sealed this 9th day of November, A. D., 1915.

'J. T. NEWTON,

Acting Commissioner of Patents. 

